Germicidal compounds



Patented Oct. 8,119.0

UNITED- STATES cnamcmar. corrrotmns' Carl Johnson, Maplewood, N. 1., andWilliam M. Allison, New York, N. Y., assignors to Oakite Products, Inc.,a corporation of New York No Drawing. Application July 2'1, 19.35,Serial No. 33,602

6 Claims.

The invention relates to germicidal compounds, and further to detergent,disinfecting and deodorizing mixtures containing such compounds.

A considerable number of materials having germicidal action, andwhich'maybe used in various cleaning processes where both cleaning andsterilizing are to be accomplished in one operation, have heretoforebeen used. However,

I such materials have been unsatisfactory for vari- 10 ous reasons- Forexample, chlorine is frequently used but constant additions of chlorine,compounds are necessary in order to maintain the germicidal property ofcleaning solutions. Other materialsare unsatisfactory, as they mayattack the articles being cleaned .or have other disadvantageousproperties.

One object of the present invention is to provide an odorless materialto be used in cleaning which is inert to, and is not affected by, the

miscellaneous inert organic materials with which it comes in contactjandwhich acts only on bacteria and other living micro-organisms at any pHvalue of the cleaning solution that may be desired. There are a numberof advantages 'in a solution having such properties.

In the first place, the solutions made according to the invention remainsterile at all times and need not be used immediately after they havebeen made. They possess substantially the same bactericidal propertiesat the end of the cleaning operation as at the beginning, at least ifthere has been no great dilution of the solution during the cleaning;Large amounts oforganic matter removed during the cleaning process donot appear to affect the sterilizing power of the solution.

A' further advantage is that the sterilizingpower may be easilydetermined at any time since it remains constant where there isnodilution, simply by determining the alkalinity or acidity which willindicate'the extent of dilution.

o of alkali are required only to retard the growth.

of bacteria, since the cleaning alone can be accomplished byconcentrations of 1% or lower.,

These strong alkali solutions will however react withand corrode theglass. Therefore, a further 55 object of the invention is to provide asuch asaz'sulfonic acid or one of its salts.

' product.

'sulfonic acid salt, which will not have the same corrosive effect as analkali. 1

which will have a minimum reaction with the articles being cleaned, andwhich therefore may be used with detergents of such low concentration asnot to destroy the articles.

A further object of the invention is to provide a material which isinexpensive and the use of which involves a relatively small amount oflabor. In prior art processes, costly apparatus has been necessary tocontrol the application of sterilizing materials and methods, thematerials used 10 have been effective only for a short time, and havenot been dependable. A further object of the invention is to provide amaterial in which considerations of tempera- .ture may be avoided, thusmaking accurate ll control of this feature of the cleaning processunnecessary.

The present invention contemplates a series of new compounds which havegermicidal action, and furthermore an admixture of such com- 20 poundswith a detergent which results in a further increase in the germicidalpower.

We have found that an.organic germicide which is...either a base or asalt, and which is aromatic, will react with a sulfonic compound, 25

The reaction may take place either between an acid and a base; an acidand a salt, a salt and a base, or two salts. Preferably an aliphaticsulfonic compound is used, although the aromatic com- 30 pounds willalso react to produce this type of The resulting product is obviously aAmongthe materials which may be used as 86 organic germicides arearomatic mercuryl compounds which are toxic to bacteria, such as phenylmercuric hydroxide, phenyl mercuric nitrate, phenyl m'ercuric chloride,para nitro toluene mercurici'cetate, alpha nitro naphthalene mer- 4oCurio acetate, alpha naphthyl-amine mercuric acetate, and the like. Inother words, these compounds are aromatic mercuryl hydroxides, orderivatives or salts thereof, which are hereinafter referred to asaromatic mercuryl compounds-or 45 organic mercury germicides. Thepreferred compounds are those mercury germicides which have the ggler'alformula Rr-HgX in which R is an arylradical and X is an acid radical ora hydroiwl group. The germicidal power of all such compounds,andparticularly of the mercuryl compounds, is increased by theircombination with the sulfonic compounds. 1 Among the sulfonic compoundswhich may be used, we prefer to use the aliphatic compounds such as thealiphatic sulfonic acids, aliphatic acid sulfates, higher fatty acidamido sulfonic acids, higher fatty acid esters of sulfonated aliphaticamido compounds or the higher fatty acids altered in other ways toprevent reaction of the carboxyl group, the acid sulfates or sulfonatesof the higher alcohols containing at least 8 carbon atoms and sulfonatedhigher fatty acids,

The highest bactericidal activity is obtained where the two compounds tobe combined are present in substantially molecular proportions, so thatno excess of either remains in the product.

' This is particularly true where the two are added to water to producea germicidal solution for use, with or Without detergents.

The process of producing these compounds may be carried out for instanceaccording to one of the following examples:

1. 389 grams of methyl-oleamide-ethyl-sulfonic acid and 295 grams ofphenyl mercuric hydroxide are reacted together, yielding 666 grams ofmethyl oleamide ethyl phenyl mercuric sulfonate and 18 grams of water.

2. 238 grams of decyl hydrogen sulfate are reacted with 295 grams ofphenyl mercuric hydroxide, yielding 515 grams of decyl phenyl mercuricsulfate and 18 grams of water.

3. 295 grams of phenyl mercuric hydroxide and 173 grams of sulfanilicacid are reacted, yielding 450 grams of phenyl mercuric sulfanilate and18 grams of water.

4. 407 grams of amino sulfon phenyl mercuric chloride and 195 grams ofsodium sulfanilate are mixed together in water. The resulting productcontains 543 grams of amino sulfon phenyl mercuric sulfanilate and 59grams of sodium chloride.

The above yields are theoretical yields which are obtainable in actualpractice because the reactions involved are neutralizing reactions ordouble decomposition reactions resulting in the formation of water or aneutral salt. The product may be recovered by evaporating the water,alcohol, or other solvent used as a reaction medium, as any neutralinorganic salt such as sodium chloride is not detrimental to theproduct. It is not necessary that the reacting materials be completelydissolved in the reacting medium as the materials will react merely bydigesting them together in the specified proportions in an aqueous oralcoholic medium, after which the resulting product may be filtered anddried.

We have found that such compounds are much more effective in theirgermicidal action than the combined effects of the individualconstituents. Tests of the constituents and of the final compounds weremade in the following manner:

. A sample of water was treated with the various mixtures, and thissample was then contaminated with some bacteria culture. It was foundthat the control solution contained approximately 5000 bacteria permilliliter. test solution was plated in a Petri dish on nutrient agarmedium for 48 hours at 37 C., and then the colonies, if any, which haddeveloped were counted.

The following tables indicate the efficiency of the various materials sotested:

The following mercury compounds, due to their slight solubility, wereused in the form of saturated aqueous solutions.

Count after- Germicide, parts per million 5 10 minute minutes minutesTrisodium phosphate 7500 and para nitro toluene mercuric acetateTrisodiurn phosphate 7500 and para nitro toluene mercuric acetate andmethyl oleamide ethyl sodium sulfonate l0 'Insodium phosphate 7500 andalphanitro naphthalene mercuric acetate Trisodium phosphate 7500 andalpha nitro naphthalene mercuric acetate and methyl oleamide ethylsodium sulfonate 10 Tnsodlum phosphate 7500 and alpha naphthylaminemercuric acetate l0 0 O 'lrisodium phosphate 7500 and alphanaphthylamine mercu icacetateandmethyl oleamide ethyl sodium sulfonate10 0 0 0 According to a further feature of the invention, we havediscovered that the germicidal effectiveness of these new compounds isstill further increased by admixture with a detergent, and particularlywith an alkaline detergent. As suitable materials may be mentioned suchalkalies or alkaline salts ,as caustic soda, sodium carbonate, disodiumphosphate, sodium tetraborate, sodium metaborate, sodium metasilicate,and sodium orthosilicate, and corresponding potassium compounds andammonium compounds wherever these exist. However, for certain types ofcleaning operations, acids or acid salts having a detergent action maybe employed, such as hydro- One milliliter of the a Only arelativelysmall proportion of the germicide .is necessary to reach suchresults. The

germicide does not exceed 10%, and'preferably is not over 1 or 2% of thedetergent. In addition to the examples given in the table, mixtures maybe provided in which the germicide and the sulfonic compound are mixedwith the detergent, and permitted. to react and form the new compoundwhen the mixture is added to water for use.

In the washing of bottles in the machine generally used for thatpurpose, we prefer a composition having as a detergent base amixturecontaining a considerable proportion of caustic soda.

This mixture also contains soda ash, trisodium phosphate and, possibly,sodium meta-silicate. When a small quantity of a germicidal compoundproduced according to the invention is added, it is possible to use sucha cleansing material in a concentration of one ounce to the gallon,where four ounces have heretofore been necessary for obtainingsatisfactory germicidal action. The mixture may contain as much as usedeither with the new compounds or with the germicidal compound-detergentmixtures.

The compounds and mixtures described above are stable and eifectiveinsolutions at relatively high temperatures throughout the entire pH 5range. In fact, their germicidal activity increases at elevatedtemperatures.

It is not necessary that the compounds heretofore described be formed inadvance of the cleaning operation. For example, the i'ngredil0 ents'maybe mixed in dry form and allowed to react only when they are dissolvedin water to form the cleaning and disinfecting solution. We may forinstance mix an organic germicide and a sulfonic compound, with orwithout a detergent 1 and/or an active oxygen compound, in the drystate. As soon as sucha mixture is added to water the materials willreact to produce the new compounds.

The terms detergent" and' "alkaline deter- 20 gent" as used herein areintended to mean not only the specific compounds listed above but alsosuch mixtures and combinations thereof as may be useful for any specificcleaning process, as well as other chemical compounds, acid or alka- 25line, having detergent action.

The term sulfonic compound as usedin the specification and claims isintended to cover both aliphatic and aromatic sulfonic acids and thesalts thereof, and also other materials such as the acid sulfates ofhigher alcohols or their salts.

1. A new organic mercury compound of the general formula (CsHeHg) .R1,in which R1 represents a radical of a higher fatty compound contalning asulfonic group.

'2. A new organic mercury compound of the general formula R.Hg.R.1,wherein R represents an aromatic radical and R1 represents a radical ofa higher fatty compound containing a sulfonic w emu 32A new organicmercury compound of the general formula R.Hg.R1, wherein It representsan aromatic radical and R1 represents themethyl-oleamide-ethyl-sulfonate radical.

4. Methyl-oleamide-ethyl-phenyl-mercuric sulfonate.

5. A neworganic mercury compound of the general formula R.Hg.Ri. whereinR represents an aromatic radical and R1 represents the decylso sulfateradical.

6. Decyl-phenyl-mercuric sulfate.

CARL JOHNSON. wnmsu M. ALLISON.

